Search of truncation of (N−1) electron basis containing full connected triple excitations in computing main and satellite ionization potentials via Fock‐space coupled cluster approach

A valence‐universal multireference coupled cluster (VUMRCC) theory, realized via the eigenvalue independent partitioning (EIP) route, has been implemented with full inclusion of triples excitations for computing and analyzing the entire main and several satellite peaks in the ionization potential spectra of several molecules. The EIP‐VUMRCC method, unlike the traditional VUMRCC theory, allows divergence‐free homing‐in to satellite roots which would otherwise have been plagued by intruders, and is thus numerically more robust to obtain more efficient and dependable computational schemes allowing more extensive use of the approach. The computed ionization potentials (IPs) as a result of truncation of the (N−1) electron basis manifold involving virtual functions such as 2h‐p and 3h‐2p by different energy thresholds varying from 5 to 15 a.u. with 1 a.u. intervals as well as thresholds such as 20, 25, and 30 a.u. have been carefully looked into. Cutoff at around 25 a.u. turns out to be an optimal threshold. Molecules such as C₂H₄ and C₂H₂ (X = D,T), and N₂ and CO (X = D,T,Q) with Dunning's cc‐pVXZ bases have been investigated to determine all main and 2h‐p shake‐up and 3h‐2p double shake‐up satellite IPs. We believe that the present work will pave the way to a wider application of the method by providing main and satellite IPs for some problematic N‐electron closed shell systems. © 2013 Wiley Periodicals, Inc.     

On the “Tertiary Structure” of Poly‐Carbenes; Self‐Assembly of sp3‐Carbon‐Based Polymers into Liquid‐Crystalline Aggregates

The self‐assembly of poly(ethylidene acetate) (st‐PEA) into van der Waals‐stabilized liquid‐crystalline (LC) aggregates is reported. The LC behavior of these materials is unexpected, and unusual for flexible sp³‐carbon backbone polymers. Although the dense packing of polar ester functionalities along the carbon backbone of st‐PEA could perhaps be expected to lead directly to rigid‐rod behavior, molecular modeling reveals that individual st‐PEA chains are actually highly flexible and should not reveal rigid‐rod induced LC behavior. Nonetheless, st‐PEA clearly reveals LC behavior, both in solution and in the melt over a broad elevated temperature range. A combined set of experimental measurements, supported by MM/MD studies, suggests that the observed LC behavior is due to self‐aggregation of st‐PEA into higher‐order aggregates. According to MM/MD modeling st‐PEA single helices adopt a flexible helical structure with a preferred trans‐gauche syn‐syn‐anti‐anti orientation. Unexpectedly, similar modeling experiments suggest that three of these helices can self‐assemble into triple‐helical aggregates. Higher‐order assemblies were not observed in the MM/MD simulations, suggesting that the triple helix is the most stable aggregate configuration. DLS data confirmed the aggregation of st‐PEA into higher‐order structures, and suggest the formation of rod‐like particles. The dimensions derived from these light‐scattering experiments correspond with st‐PEA triple‐helix formation. Langmuir–Blodgett surface pressure–area isotherms also point to the formation of rod‐like st‐PEA aggregates with similar dimensions as st‐PEA triple helixes. Upon increasing the st‐PEA concentration, the viscosity of the polymer solution increases strongly, and at concentrations above 20 wt % st‐PEA forms an organogel. STM on this gel reveals the formation of helical aggregates on the graphite surface–solution interface with shapes and dimensions matching st‐PEA triple helices, in good agreement with the structures proposed by molecular modeling. X‐ray diffraction, WAXS, SAXS and solid state NMR spectroscopy studies suggest that st‐PEA triple helices are also present in the solid state, up to temperatures well above the melting point of st‐PEA. Formation of higher‐order aggregates explains the observed LC behavior of st‐PEA, emphasizing the importance of the “tertiary structure” of synthetic polymers on their material properties.     

On the structure of split Leibniz triple systems

We study the structure of arbitrary split Leibniz triple systems with a coherent 0-root space. By developing techniques of connections of roots for this kind of triple systems, under certain conditions, in the case of T being of maximal length, the simplicity of the Leibniz triple systems is characterized.     

Linear Group 13 E≡E Triple Bonds in E2Li62+

The triply bonded heavier main-group compounds have a textbook trans-bent geometry, in contrast to a familiar linear form found for the lightest analogues. Strikingly, the unexpected linear group 13 E≡E triple bonds were herein found in the D_4h-symmetry E₂Li₆²⁺ clusters, and they possess a large barrier (>18.0 kcal/mol) towards the dissociation of Li⁺. The perfectly surrounded Li₄ motifs and two linear coordinated Li atoms strongly suppress the increasing nonbonded electron density of heavier E atoms, making two degenerate π bonds and one multi-center σ bond in linear heavier main-group triple bonds. The surrounding Li₆ motifs not only creates an effective electronic structure to form a linear E≡E triple bond, but the resulting electrostatic interactions account for the highly stable global E₂Li₆²⁺ clusters.     

Metabolite Profiling and Characterization of LW6, a Novel HIF-1α Inhibitor,as an Antitumor Drug Candidate in Mice

A novel HIF (hypoxia-inducible factor)-1α inhibitor, the (aryloxyacetylamino)benzoic acid derivative LW6, is an anticancer agent that inhibits the accumulation of HIF-1α. The aim of this study was to characterize and determine the structures of the metabolites of LW6 in ICR mice. Metabolite identification was performed using a predictive multiple reaction monitoring-information dependent acquisition-enhanced product ion (pMRM-IDA-EPI) method in negative ion mode on a hybrid triple quadrupole-linear ion trap mass spectrometer (QTRAP). A total of 12 metabolites were characterized based on their MS/MS spectra, and the retention times were compared with those of the parent compound. The metabolites were divided into five structural classes based on biotransformation reactions: amide hydrolysis, ester hydrolysis, mono-oxidation, glucuronidation, and a combination of these reactions. From this study, 2-(4-((3r,5r,7r)-adamantan-1-yl)phenoxy)acetic acid (APA, M7), the metabolite produced via amide hydrolysis, was found to be a major circulating metabolite of LW6 in mice. The results of this study can be used to improve the pharmacokinetic profile by lowering the clearance and increasing the exposure relative to LW6.     

基于包层模谐振的三包层石英特种光纤温度传感特性研究

提出了一种基于包层模谐振的光纤温度传感器. 它是通过将三包层石英特种光纤(TCQSF)两端分别与普通单模光纤(SMF)电弧熔接构成的SMF-TCQSF-SMF结构. 根据耦合模理论, 首先将TCQSF等效为三个同轴波导, 按各波导模场的分布特点标量计算其传输模式的色散曲线, 并深入研究其耦合长度与传输谱线之间的关系; 其次根据光纤的热光效应及热膨胀效应, 分析计算该传感器的温度灵敏度; 最后选取耦合长度为一个拍长时的传感器进行温度传感实验. 实验结果表明, 在35-95 ℃的温度变化范围内, 其温度灵敏度为73.74 pm/℃, 与理论计算结果一致. 因此, 该传感器具有结构简单、制备容易、灵敏度高、包层模激发可控等优点, 可用于工业生产、生物医学等温度传感领域.     

Biembedding Steiner Triple Systems in Surfaces Using the Bose Construction

A uniform framework is presented for biembedding Steiner triple systems obtained from the Bose construction using a cyclic group of odd order, in both orientable and nonorientable surfaces. Within this framework, in the nonorientable case, a formula is given for the number of isomorphism classes and the particular biembedding of Ducrocq and Sterboul (preprint 18pp., 1978) is identified. In the orientable case, it is shown that the biembedding of Grannell et al. (J Combin Des 6 ( 7 ), 325–336) is, up to isomorphism, the unique biembedding of its type. Automorphism groups of the biembeddings are also given.     

Large Cross‐Free Sets in Steiner Triple Systems

A cross‐free set of size m in a Steiner triple system is three pairwise disjoint m‐element subsets such that no intersects all the three ‐s. We conjecture that for every admissible n there is an STS(n) with a cross‐free set of size which if true, is best possible. We prove this conjecture for the case , constructing an STS containing a cross‐free set of size 6k. We note that some of the 3‐bichromatic STSs, constructed by Colbourn, Dinitz, and Rosa, have cross‐free sets of size close to 6k (but cannot have size exactly 6k). The constructed STS shows that equality is possible for in the following result: in every 3‐coloring of the blocks of any Steiner triple system STS(n) there is a monochromatic connected component of size at least (we conjecture that equality holds for every admissible n). The analog problem can be asked for r‐colorings as well, if and is a prime power, we show that the answer is the same as in case of complete graphs: in every r‐coloring of the blocks of any STS(n), there is a monochromatic connected component with at least points, and this is sharp for infinitely many n.     

The Order of Automorphisms of Quasigroups

We prove quadratic upper bounds on the order of any autotopism of a quasigroup or Latin square, and hence also on the order of any automorphism of a Steiner triple system or 1‐factorization of a complete graph. A corollary is that a permutation σ chosen uniformly at random from the symmetric group will almost surely not be an automorphism of a Steiner triple system of order n, a quasigroup of order n or a 1‐factorization of the complete graph . Nor will σ be one component of an autotopism for any Latin square of order n. For groups of order n it is known that automorphisms must have order less than n, but we show that quasigroups of order n can have automorphisms of order greater than n. The smallest such quasigroup has order 7034. We also show that quasigroups of prime order can possess autotopisms that consist of three permutations with different cycle structures. Our results answer three questions originally posed by D.  Stones.